JPS63218670A - 2-(2',4'-dihydroxyphenyl)-4-methoxy-5-(3-methylbutyl)-6-hydroxy-coumarone and quality preservative - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula. USE:A quality preservative useful in the fields of foods, cosmetics, drugs, stock raising and fisheries since the compound has both antioxygenic action and antimicrobial action and is tasteless and odorless. PREPARATION:Licorice root or a water extracted residue thereof (e.g. residue after extraction of glycyrrhizin from Licorice root) is immersed in an organic solvent such as methanol, acetone, petroleum ether, benzene or ethyl acetate, heated under reflux or immersed in the organic solvent at normal temperature, the solvent is distilled away from the obtained extracted solution, the extract is dissolvent in a lower aliphatic alcohol and subjected to chromatography using silica gel to give a compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel malone derivative having the following structural formula (I) and a quality preservation agent containing the same as an active ingredient.

2-(2',4'-dihydroxyphenyl) represented by
This invention relates to -4-methoxy.5-(3-methylbutyl)-6-hydroxy-coumarone and a quality preservation agent comprising this compound.

Conventional Technology There are two main causes of deterioration in product quality in the fields of food, cosmetics, pharmaceuticals, livestock farming, fisheries, etc.: oxidation and putrefaction. The former mainly occurs as a chemical reaction due to oxygen in the air, and the latter occurs as a biological reaction due to the growth of microorganisms. However, these two are not clearly separated, and oxidation may proceed due to enzymatic reactions caused by the growth of microorganisms.

Generally, antioxidants are used to prevent oxidation, and antibacterial agents are used to prevent spoilage, but it is difficult to prevent spoilage with antioxidants or oxidation with antibacterial agents. Therefore, in order to maintain the quality of the product, it is necessary to use individual inhibitors, which poses the problem of increasing the amount of additives.

It is known that the organic solvent extract of licorice has antioxidant power (Journal of Japan Food Industry Association; TJG Vol. 25, No. 25, 1).
978), and is also known to have antibacterial properties (Japanese Patent Laid-Open No. 5
9-46210). Therefore, if the organic solvent extract of licorice is effectively used, it is possible to achieve both antioxidant and spoilage prevention. Several studies have been conducted on the antioxidant and antibacterial components of organic solvent extracts of licorice, and the journal of Japan Food Industry Association; Vol. 29, No. 7, 19
82, a brown melanoidin-like substance with a molecular weight of 10,000 or more was disclosed as an antioxidant component, and
-190784 states that the antioxidant component and the antibacterial component are separate and can be separated using a basic ion exchange resin or the like.

Furthermore, the Journal of Pharmacological Sciences; 40 (4), 406.1986 discloses four ingredients, glycilol, inglycilol, glycine, and glycicumarin, as antibacterial ingredients against caries-causing bacteria.

As described above, organic solvent extracts of licorice are useful as antioxidants and antibacterial agents, but their use is currently limited due to their reddish-brown color and unique odor.

Means for Solving the Problems The present invention provides a novel compound 2-(2',4) obtained from licorice.
'-dihydroxyphenyl)-4-methoxy 5-(3
-Methylbutyl)-6-hydroxy coumaron and a quality preservation agent comprising this compound have achieved the above-mentioned object.

That is, the present inventor has been researching antioxidant substances and antibacterial substances obtained from licorice, and found that by purifying the components extracted using an organic solvent by chromatography using silica gel, Sephadex, etc. (I
The present invention was completed by isolating a novel compound represented by the formula () and discovering that it has strong antioxidant and antibacterial properties and can be effectively used as a quality preservation agent.

The novel compound 2-(2',4'-dihydroxyphenyl)-4-methoxy-5-(3-methylbutyl)-6-hydroxy-coumaron according to the present invention has a chemical structure represented by the above formula (I). It is a colorless acicular crystal and has the characteristic values described below.

The novel compound of the present invention is obtained by extracting licorice or its aqueous (or aqueous medium) extract (for example, the residue after extracting glycyrrhizin from licorice) with the following solvents: methanol, ethanol, etc. Lower aliphatic alcohols; Lower aliphatic ketones such as acetone; Lower aliphatic ethers such as dioxane and ethyl ether; Volatile hydrocarbons such as petroleum ether, n-hexane, cyclohexane, toluene, and benzene; Number of carbon atoms such as methylene and chloroform is 1
~4 halogenated hydrocarbons; esters having 3 to 7 carbon atoms such as ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate; and mixtures of two or more of these solvents.

Extraction with the above organic solvent involves immersing the raw material to be treated in about 3 to 5 times the volume of the organic solvent and heating it under reflux.
This is carried out by immersion in O times the amount of organic solvent at room temperature.

Purification of the novel compound of the present invention from an organic solvent extract involves distilling off the solvent from the organic solvent extract, dissolving the extract in a lower aliphatic alcohol such as methanol or ethanol, and then chromatography using silica gel or Sephadex. This is done by

The licorice used in the present invention is preferably licorice from Tohoku, northwest, or Mongolia, and licorice from Xinjiang or the Soviet Union is not preferred.

The compound of the present invention is tasteless and odorless, and is effective in maintaining the quality of products in all fields of food, cosmetics, pharmaceuticals, livestock industry, fisheries industry, etc.

The suitable amount of the compound of the present invention to be added can be arbitrarily selected depending on the desired quality retention period, but in many cases
．． 0003-0.035% by weight, preferably 0.002
Good results can be obtained by setting the content to 5 to 0.02% by weight.

In addition to being used alone, the compound of the present invention can also be used with existing antioxidant substances such as tocopherol, BHA, BHT, gallic acid and its derivatives, ascorbic acid and its salts, citric acid and its salts, or EDTAB and its salts, Existing antibacterial substances such as sorbic acid, glycine, condensed phosphates, ethanol, propylene glycol,
Can be used in combination with lysozyme, glycerin fatty acid ester, sucrose fatty acid ester, sodium acetate, organic acids, etc. The quality-preserving effect of the compounds of the present invention is not adversely affected by these compounds, but rather may be further enhanced by a synergistic effect.

Example The present invention will be explained below with reference to Examples.

Example 1 2-(2',4'-dihydroxyphenyl)=4-methoxy-5-(3-methylbutyl)-6 by the following method
-Hydroxy-coumaron was produced.

3.5 kg of licorice from northwest Japan was heated under reflux for 2 hours with 17.511 chloroform to extract chloroform-soluble components. The solvent of this extract was distilled off, and it was further dissolved in 50% ethanol, and the 50% ethanol soluble portion was approximately 50 g.
I got it. This 50% ethanol soluble material was fractionated with normal phase silica gel (chloroform:methanol-40:1),
Next, it was treated with Sephadex LH-20 and 2-(2'
,4'-dihydroxyphenyl)・4-methoxy・5-
(3-Methylbutyl)-6-hydroxy-coumarone 8
I got 2B. The obtained compound exhibits the following properties and instrumental analysis values.

Molecular formula: Ct. HzoOs Molecular weight: 340.38 Properties: Colorless acicular crystals Elemental analysis: Calculated value (%) C; 70.5B, H; 5.
92 Actual value (%) C; 70.04 H; 5.90
Melting point: 183-186°C I Ry2:2 am-': 3350,16
H, 1600, 1510, 1320, 180, HHUV
λ:::'nm(E lj : 3!1(1157,
5), 336 (992,5) MS tact: 34
0,2g5j14,270,269'H-NMRδ(p
pm) (CD30D): xro+utic ABX series,
7.56(d, J=L(Hx)645(dd, J=1
411g, 2,2■! ; d, J-2Hx) sro+u
tic singlet, 7.151ar*nic
5iBlet, 6.70isopentenyl (
romp, 1. H, 1,73QxCH3) 344(d
J straw 9.2Ht, CHt) 5.17 (J -9,2H
x, =CL) melbox71 (ro++p,
395”C-NMRδ (ppmXd・-DMSO): 1
7.56(Q), 2130(t), ! 5.49
(Q), 5L70(Q), 92.17(d)+
0044(d), +010(d), +og, u(d
), +0111(S), +1155(S)114.
06(s), H3,91(d), H6,54(d)
, 09.30 (s), 150.06 (s) 150.
35(s), 153.1to(s), 153.11
(s), 155.23(s), 151.05(s)
Example 2 Fats and oils A-F were manufactured using the following formulations.

BCDEF Compound of the present invention low (glycycoumarin 1O2 glycyrrhizin IOB natural tocopherol IOB licorice chloroform extract IOH purified lard
1001100 (IOJ 100 (1001100) (AOM test was conducted on these oils and fats A-F, POv
The time T required for T to reach 20. The results of the measurements were as follows.

Fats and oils T2゜ (hours) A 2.4 8 48, O C3,8 D　　　　2.5 E　　　　　12. O F 10.0 Example 3 Fats and oils A-D were manufactured using the following formulations.

BCD Compound of the present invention 20B Natural tocopherol 211B Chloroform extraction of licorice 'k 20 m (rapeseed oil
100 (100 (100t) 100 (AOM test was conducted on these oils and fats A-F, and POv was 1
Time T until reaching 00. . The results of the measurements were as follows.

Fats and oils T+ao (hours) A 20. OB 32.2 CI8.0 D 24.0 Example 4 The following 1 to 3 compounds of the present invention, glycicumarin, and streptomycin sulfate as a control were tested.
The antibacterial activity of No. 7 against bacteria, yeast, and mold was tested by the following method.

1, 5taphylococcus aureus,
2. Bacillus 5ubtilis3, Es
ch@richia coli, 4. Sac
charomyces cerevisiae5, Ca
ndida utilis, 6. Pic
hia nakawawa*7. Rh1zopus f
The test bacterial solution of P. ornossnsis was prepared as follows. Bacteria (1-3) were cultured on standard agar slants for 30'03 days, and yeasts and molds (4-7) were cultured on potato dextrose agar slants at 30°C for 3 days. Immediately before use, bacteria or spores were scraped from the cultured bacteria and suspended in 5 ml of sterile physiological saline to prepare a test bacterial solution.

On the other hand, pour 1 ml of the three-compound solution at a predetermined concentration into a sterile petri dish (
9c+Blx2cm) and add 121'01 to this in advance.
Add 19 ml of standard agar medium that has been sterilized for 5 minutes, mix well, and solidify on a plate. One platinum loop plate is coated with the above test bacterial solution and cultured at 30°C. After one day, the bacteria become yeast,
The growth of fungi was observed after 3 days.

The results are shown below.

Test bacteria: Stspk71ococcms amrem
sTest bacteria: Bxcillns 5ubtilisTest bacteria: Escherichia coliTest bacteria:
Ssccbsromyces cerevisiae Test strain: C1 Otori t + Liis Test strain: Pi
cbia nakawswie Test bacterium: Rh1zop
us formose++5is (Note) Symbol 1 in the table: No colonies observed +: Colony occurrence Effect of the invention As shown in the examples, the compound of the present invention has both strong antioxidant and antibacterial effects, and has an excellent quality retention effect. There is. This quality retention ability is at a high level that cannot be achieved with conventional simple antioxidants and antibacterial agents.

Therefore, according to the present invention, it is not necessary to separately add an antioxidant and an antibacterial agent to maintain the quality of the product, and the quality of the product can be maintained in good condition by adding only a small amount.

Claims (2)

[Claims] (1) 2-(2',4'-dihydroxyphenyl)-4
-Methoxy-5-(3-methylbutyl)-6-hydroxy-coumaron. (2) 2-(2',4'-dihydroxyphenyl)-4
-A quality preservation agent containing methoxy-5-(3-methylbutyl)-6-hydroxy-coumarone as an active ingredient.